Mechanism of Palladium-Catalyzed Suzuki-Miyaura Reactions: Multiple and Antagonistic Roles of Anionic "Bases" and Their Countercations

被引：201

作者：

Amatore, Christian ^{[1
]}

Le Duc, Gaetan ^{[1
]}

Jutand, Anny ^{[1
]}

机构：

[1] Ecole Normale Super, Dept Chim, UPMC, CNRS,UMR 8640, F-75231 Paris 5, France

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 31期

关键词：

bases; kinetics; palladium; reaction mechanisms; Suzuki-Miyaura reactions; CROSS-COUPLING REACTION; OXIDATIVE ADDITION; ORGANOBORON COMPOUNDS; ARYLBORONIC ACIDS; IN-SITU; ZEROVALENT PALLADIUM; PHENYLBORONIC ACID; ARYL HALIDES; COMPLEXES; TRANSMETALATION;

D O I：

10.1002/chem.201300177

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In Suzuki-Miyaura reactions, anionic bases F- and OH- (used as is or generated from CO32- in water) play multiple antagonistic roles. Two are positive: 1)formation of trans-[Pd(Ar)F(L)(2)] or trans-[Pd(Ar)- (L)(2)(OH)] (L=PPh3) that react with ArB(OH)(2) in the rate-determining step (rds) transmetallation and 2)catalysis of the reductive elimination from intermediate trans-[Pd(Ar)(Ar)(L)(2)]. Two roles are negative: 1)formation of unreactive arylborates (or fluoroborates) and 2)complexation of the OH group of [Pd(Ar)(L)(2)(OH)] by the countercation of the base (Na+, Cs+, K+).

引用

页码：10082 / 10093

页数：12

共 88 条

[1] Mechanism of the palladium-catalyzed homocoupling of arylboronic acids: Key involvement of a palladium peroxo complex [J].

Adamo, Carlo ;

Amatore, Christian ;

Ciofini, Ilaria ;

Jutand, Anny ;

Lakmini, Hakim .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (21) :6829-6836

[2] OBSERVATION OF CATALYTIC INTERMEDIATES IN THE SUZUKI REACTION BY ELECTROSPRAY MASS-SPECTROMETRY [J].

ALIPRANTIS, AO ;

CANARY, JW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (15) :6985-6986

[3] Non-conventional methodologies for transition-metal catalysed carbon-carbon coupling: a critical overview. Part 2: The Suzuki reaction [J].

Alonso, Francisco ;

Beletskaya, Irina P. ;

Yus, Miguel .

TETRAHEDRON, 2008, 64 (14) :3047-3101

[4]

Amanda A. G. Jarvis, 2011, CURR ORG CHEM, V15, P3175

[5] Oxidative addition of aryl halides to transient anionic sigma-aryl-palladium(0) intermediates - Application to palladium-catalyzed reductive coupling of aryl halides [J].

Amatore, C ;

Carre, E ;

Jutand, A ;

Tanaka, H ;

Ren, QH ;

Torii, S .

CHEMISTRY-A EUROPEAN JOURNAL, 1996, 2 (08) :957-966

[6] INTIMATE MECHANISM OF OXIDATIVE ADDITION TO ZEROVALENT PALLADIUM COMPLEXES IN THE PRESENCE OF HALIDE-IONS AND ITS RELEVANCE TO THE MECHANISM OF PALLADIUM-CATALYZED NUCLEOPHILIC SUBSTITUTIONS [J].

AMATORE, C ;

JUTAND, A ;

SUAREZ, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (21) :9531-9541

[7] RATES AND MECHANISMS OF OXIDATIVE ADDITION TO ZEROVALENT PALLADIUM COMPLEXES GENERATED IN-SITU FROM MIXTURES OF PD0(DBA)2 AND TRIPHENYLPHOSPHINE [J].

AMATORE, C ;

JUTAND, A ;

KHALIL, F ;

MBARKI, MA ;

MOTTIER, L .

ORGANOMETALLICS, 1993, 12 (08) :3168-3178

[8] MECHANISM OF OXIDATIVE ADDITION OF PALLADIUM(0) WITH AROMATIC IODIDES IN TOLUENE, MONITORED AT ULTRAMICROELECTRODES [J].

AMATORE, C ;

PFLUGER, F .

ORGANOMETALLICS, 1990, 9 (08) :2276-2282

[9] Anionic Pd(0) and Pd(II) intermediates in palladium-catalyzed Heck and cross-coupling reactions [J].

Amatore, C ;

Jutand, A .

ACCOUNTS OF CHEMICAL RESEARCH, 2000, 33 (05) :314-321

[10] Mechanistic Origin of Antagonist Effects of Usual Anionic Bases (OH-, CO32-) as Modulated by their Countercations (Na+, Cs+, K+) in Palladium-Catalyzed Suzuki-Miyaura Reactions [J].

Amatore, Christian ;

Jutand, Anny ;

Le Duc, Gaetan .

CHEMISTRY-A EUROPEAN JOURNAL, 2012, 18 (21) :6616-6625

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